Clear and pigmented multi-component oil-in-water resin emulsion textile decorating compositions and process for preparing same



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e 2,907,720- CLEAR AND PIGIVIENTED MULTI-COMPONENT OIL-INFWATER RESIN EMULSION TEXTILE DECORATING COMPOSITIONS AND PROCESS FOR PREPARING SAME 1 Laszl Auer, South Orange,N.J., assignor to J. R. Geigy, S.A., Basel, Switzerland, a corporation of Switzerland N Drawing Application July 23, 1956 e Serial No..599,318

15 Claims. c1. 260-6) GENERAL OUTLINE OF INVENTION Textile printingand dyein'g is conventionally done with dyestuffs, which are water soluble or are developed on the fibers from water soluble intermediates. The application of dyestuffs is a multistep process and frequently the ultimate color is not visible at the stage when the fabrics leave the printing or dyeing machinery. This causes difficulties. in control and to avoid seconds needs great skill and lots of luck too.

Dyestuffs, in general, have more or less limited light fastness, particularly in light or pastel shades. The Fade-o-meter is an accepted apparatus to measure light fastness in an accelerated manner. Whereas automobile lacquers, or resin finishes are required to be fast to Fade-o-meter exposure for 1000 hours, dyed fabrics or fabrics printed with dyes, fade in less than 48 hours, in most cases, and 10 to 20 hours exposure fastness has to be accepted with many shades.

Pigments, in general, are more light fast than dyes, and therefore pigment printing and pigment dyeing has been the aim of the art since quite some time. As pigments are dry powders and insoluble in water or organic solvents, they have to be adhered to thefabric by a resinous binder. A particularly successful binder for pigments was found in the combination of Oil modified alkyd resins and organic solvent soluble aminoaldehyde resins, such as butyl modified urea formaldehyde resins or butyl modified melamine formaldehyde resins. For printing, water-in-Oil emulsion colors are used, whereas for solid color dyeing, it is customary to use oil-in-water emulsions. .The oil phase of such emulsions consists of the binder resin, usually comprising an alkyd resin component and an amino-aldehyde resin component, in the presence or absence of organic solvents. The pigments may be incorporated either in the oil phase or the water phase.

The general drawback of pigment colors is their crocking. Crocking is marking off by abrasion onto an unprinted and not dyed portion of the fabric, or onto fabric in general. The crocking of pigment colors is their main drawback, which prevents increase in their use for coloring textiles. Also, the washability and dry cleaning resistance of pigment colored fabrics requires improvement, particularly if high temperatures of curing are to be avoided. Textile plants have low pressure 2,907,720 Patented Oct. 6, 1959 steam available and for curing or thermosetting the amino-aldehyde resins temperatures of 275 to 300 F.

are needed. a

In present day textile printing with pigments water-inoil emulsions are used in the trade, in spite of the fact that solvent cleaning of equipment is troublesome in textile plants. f

Oil-in-water emulsions are easier to handle in textile plants than Water-in-oil emulsions. They could 'be washed from the printing rollers, color boxes, doctor blades, brush rollers, etc. with water. They also could be washed from back-grays, rubber blankets with ease. There are two reasons why there was no oil-in-water type printing color on the market prior to the instant development: (1) emulsifying agents which are suitable to. produce oil-in-water emulsions and the. necessary protective colloids, which secure stability, both reduce the washability of pigment prints. Present day binders do not take such reduction successfully. (2) If the same quality of pigment color is dispersed in an oil-in-water emulsion color concentrate and in a water in-oil color concentrate, and both are reduced in varying proportions with clear cut-backemulsions, the water-in-oil emulsion printing colors take more reduction to yield a certain shade, than oil-in-water emulsions. The reason is probably explained by the fact that most pigments are hydrophobic and organophilic, flush into the oil phase, and if the color bearing oil phase is the continuous phaseof the emulsiombetter mileage is obtained, pound for pound of color. As the pigment colors are the most expensive ingredient of printing emulsion colors, economic factors excluded up to now the use of oil-in-water emulsions for printing, whereas they are used regularly for pigment padding, to obtain solid shades. I

In accordance with this invention, improvement is achieved in making oil-in-water emulsion pigment colors by using fatty acid ester resin binders which are emulsion polymerized or emulsion, aggregated. .The instant invention is a continuation-in-part of copending applications SerialNos. 739,945, filed April 7, 1947, now Patent No. 2,530,370; 91,009, filed May 2, 1949, now Patent No. 2,637,621; 169,791, filed June 22, 1950, now Patent No. 2,637,711; and 180,700, filed August 21, 1950, now Patent No. 2,637,705. By the use of such resin binders advantages result in faster solidifying binders, increased toughness and better aging qualities of the prints obtained.

As binder resins the following may be mentioned as suitable: condensation products of bis-phenol and epichlorhydrin esterified with fatty acid esters. Organic solvent soluble urea and melamine formaldehyde resins may be present in the emulsions to further toughen the binder resins.

The emulsion polymerized or emulsion aggregated oilin-water emulsions of fatty acid esters are described in my copending application Serial No. 739,945, now Patent No. 2,530,370, above referred to. To prepare such emulsions, the fatty acid esters are bodied to a relatively heavy viscosity and then emulsified. The dispersed phase of such emulsions is the fatty acid ester. The dispersed phase particles of such emulsions are then aggregated by employing hydrogen peroxide, or in other ways as described in said copending application. The degree of aggregation of the dispersed particles in situ is such as to render the emulsion highly sensitve to the action of air when spread in thin films and thereby provide for the formation of a coherent solid film immediately upon demulsification of the emulsion. Advantageously the pH value of the emulsionis retained within certain limits during the aggregation treatment. Improved results are obtained by the treated emulsions of this specification if the increase in oxygen content of the solidified fatty acid esters is kept low, when compared with the oxygen con- Mannitol .011 and cinema 011. Such esters may be further modified 40 I found that the reaction extremely slow with r 7 3 tent or the same esters before emulsification and emulsion aggregation.

STARTING MATERIALS Typical of the oils, the fatty acids of which may form 5 the esters used 'in'this process are as follows: Tung oil Oiticic'a oil Dehydrated castor oil Linseed oil Perilla'oil s'u'n'flowe'r Oil Poppysee'd oil So'ya 'bean 'oil Walnut oil g Rapeseed oil messed oil Oliveoil Cottonseed oil Coconut oil Babas's'u oil Hydroxylated oils such as castor oil, etc. Fish oils (train oils) the following polyhydric alcohols are suitable for p'roduin'g esters with'the above fatty acids:

Glycerin I Pentaerythritol Sorbitol Alcohols formed by the condensation of bis-phenol and epichlorhydrin Certain polyglycols,-amongst others Particularly advantageous results were obtained with the condensation products of bis-phenol and epic hlorhydrin, esterfied with fatty acids, such as dehydrated castor oil fatty acids or mixtures of the fatty acids of soyabean bysty'ren'ating them. i 'The above described fatty acid esters may be toughened by the addition of organic solvent soluble amine aldehyde resins formed with urea'or melamine or al-kylated or etherified urea and melamine.

A 'few examples are given of commercially manufactured resins useful in "the instant process:

E'p'ichlorliydrin and bis-phenol condensation product (alcohol): Epon I004. Dehydrated castor oil fatty acid ester of Ep'o'n I004: Epitex 1 20.

Organicsolvent soluble amino-aldehyde resins: Melmac 245-8, Melmac 248-8.

I found that in my .process best results are obtained withpolyhydric alcohol esters of acids of fatty oils, which e's'ters contain in their acid component at least 50% acids of fatty oils and which fatty I oil acids comprise fatty acids having at least two double bonds.

Any appropriate mixtures or combinations-ofmembers of the above described classes may be treated, as de sired. p I

Thebetter drying a fatty oil is, the more suitable it is for mypresent process. I found that at least some of the fatty acids present in my esters should preferably contain more than one doublebond in the molecule. This inchides estersof the drying oil fatty acids and of the semidrying oil fatty acids. I'alsfo found that esters'of fatty a'cidsh'aving conjugated double-bonds more easily undergo my emulsion aggregation process, than fatty acids with isolated double bonds.

EMULSION AGGREGATION The fatty'ac'id esters are b'o'died'to a suitable viscosity before 'e'rnul'sification, and my 'co'pending application Serial No. 39,945, 'n'owPat'e'nt No. 2,530,370, describes the ammonia test'which is very suitableto determine satis- 4 factory viscosity. The sulfur test described in the same specification is another suitable method.

The emulsion polymerization or emulsion aggregation process and its reaction conditions is described in detail in copending application Serial No. 739,945, now Patent No. 2,530,370. The aggregating agent is oxygen. I believe that the active agent of my process is anelectrically charged oxygen particle. However, I have no definite proof of that supposition. As not any and all oxygenmay act in my process as aggregating agent, I shall "referfto the oxygen which is suitable in my process as active oxy-j gen and I believe that the particles'of this active'oxyg'en are most probably electrically charged.

I can obtainmy active oxygen in various ways; (1) I may use a peroxide, such as a metal peroxide of hydrogen peroxide, or organic peroxide to supply my active oxygen to my emulsions. (2) 'I may blow oxygen or an oxygen containing gas, such as air, through my emulsions.

(3.) I may use the oxygen which is present 'in the water phase of my emulsion as-absorbed oxygen. 7

Application of heat accelerates the action of the oxygen. Usually temperatures between 50 -C. and -C. are useful for such acceleration. Agitation of the emulsion also accelerates the process.

' In case peroxides are used and oxygen is liberated in situ, further activation by agitation and/or heat is not a necessary requirement and the aggregation may' be carried out in a satisfactory way at room temperature and even at temperatures lower than room temperature.

The concentration of the "emulsion influences' t'he rate of reaction. The 10% to 20% non-volatile containing emulsions will produce solidified particles faster than a 70% solid content emulsion. Very satisfactory results can be obtained around 50% non-volatile content.

Advantageous pH limits Oneof the importantcriterio'ns of my process is the p'I-I of the emulsion. I found that it is important'to have critical pH limits to carry out my process satisfactorily.

and there is a very slow range from about a pH of "5.7 to about 8.4. The range is very active below 5.7, s'u'chxas for instance in theneighborhood of pH of 2.8 and also above 8.4, forinstance in the region of pH of 10.5 and higher. In other words, the reaction is greatly accelerated by thepH values below 5.7 or above 8.4. However, for many purposes, if working on the alkaline side, I found it to beadvantageous'to have a pH of at least 10, and if working on the acid side, "to have a pHwhich does not exceed 4.

It has been found that metallic driers accelerate the emulsion aggregation process particularly in such "cases in which the aggregation is carried 'out in an alkaline medium. Therefore, if metallic drie'r's are desired to be present in the fatty acid esters, it is of advantage to work on the alkaline side. However, if the absence of metallic driers is desired, a conversion in anemulsion on the acid side 'is more desirable. Further, it may be mentioned that conversion on the acid side is advantageous if a constant pH is desired. In case of emulsion aggregation on the alkaline side, thepH generally changes insofar as it-gradually becomes lower.

In the illustrative examples of this specification, the process will be demonstrated on emulsions which are on the alkaline 'side'of'the pH range. This is r'neant'to illustrate the process only and "not to limit same.

Oxygen supplying agents As mentioned further above, if other-reaction conditions are .proper, the oxygen content of the water, present in the' emulsion, may be satisfactory.

Oxygen may be supplied to theemulsion in the form of oxygen gas or'oxygen containing gases, such air, by bubbling through the emulsion such gases or by ina used, such as sodium peroxide, barium peroxide, mag-.

nesium peroxide, zinc peroxide, other metal peroxides,

or organic peroxides, such as benzoylperoxide urea peroxide, etc. Examples of per-compounds are further perborate s, percarbonates, persulfates, such as potassium, sodium and ammonium persulfates, perchlorates, pyrophosphate peroxides, ozonides, 'etc. The criterion of the usefulnesssof these agents is that they should supply oxygen in 'situ under the reactionconditions applied in my process and that the emulsion could be prepared in such a way that, it should not break in their presence.

Oxygen content In my process the oxygen content of the emulsified fatty acid esters increases very little, if any, during the emulsion aggregation process. The oxygen content increase is notmore than 2.8% and advantageously not more th3.l1yl.5%. In mostcases the oxygen content increase is less than p p EMULSIFYING AGENTS Great variety of emulsifying agents may be used in my process. A list of such emulsifying agents is given,-

for instance, under the titleof Surface-Active Agents in the January 1943issue of Industrial and Engineering Chemistry, 011 pages 126 to 130. a

Soaps of fatty acids are for instance satisfactoryemulsifying agents. A list of some others is given herewith:

1- Trade Name; Manufacturers Description Duponol ME--.

Fatty alcohol sulphate, sodium salt. Aerosol '11.-.

Dioctyl ester of sodium sulphosuccinic acid.

Emulphor AG-- Ethylene oxide fatty acid condensate (poly- A glycol ester of long chain fatty acid, oleic j 1 acid type). Igcponi Sodium sulphonate of an oleic acid'ester of an aliphatic compound, for instance, of the type i 11HaaC0N(OH3)C2H4SO Na.

Triton 720 and 770. Sodium saltof aryl alkyl poly ether sulphonate.

PIGMENT USED .IN MAKING WATER .DISPER- .SIONS The organic pigments used. herein are usually prepared by precipitation methods. They are all water insoluble. As starting material for this invention either a filter press cake or dry powder can be used. Carbon black, if used, is not made by precipitation method and is used as dry powder in the process.

The following groups of pigments exemplify, but do not limit the scope of the starting materials of this invention:

V (l) Phthalocyanine pigments Phthalocyanine blue, which is a copper or tin-copper phthalocyanine, is marketed under trade names of Monas'tral Fast Blue and as Heliogen Blue.

Phthalocyanine green, which is a chlorinated copper phthalocyanine. color,is marketed under trade names of Monastral Fast Green, and as Heliogen Green.

4 Benzidine Yellows are couplings between dichlorobenzidine and acetoacetic arylides, such as the .acetoaceticauilide, -ortho toluidide, -xylidide,

para chloro auilide and -ortho chloro auilide. L

Benzidine orangeis a coupling productof dichloro benzidine with pyrazolone substitution methyl phenyl pyrazolone. v u

'Hensa Yellows are acetoacetic arylide 'couplingsfwith substituted anilines, like 4-chloro-2-nitroaniline, or orthonitroaniline, amongst others.

Insoluble A zo Reds are coupling products of the Naphthol AS type compounds of beta-ortho-naphthoic acid, such as Naphthol AS, Naphthol AS-OL, Naphthol AS-BS, Naphthol AS-D with fast color salts, such as 2,5 dichloroaniline, p-nitro-orthotoluidine, p-nitro-orthof Vat pigments, are of the indigoid or anthraquinone type. The indigoid typeincludes thioindigo derivatives and the anthraquinone type includes derivatives of Flavanthrone, Benzanthrone and complex structures made by condensing benzanthrone molecules. v

Thioindigo Red B .has Color Index. No. 1207 an Schultz No. 912. For formulation, i.e. structural formula see pages 206 and 209 in Pratt: Chemistry and Physics of Organic Pigments, John Wiley & Sons, 1947.

Idanthrene Blue with Color Index No. 1106, Schultz No. 837 is an example of the anthraquinone type vat pigments. t 1

Structural formulas of some vat pigments are listedon pages 429 to 435 in volume V of Mattiollo: Protective and Decorative Coatings, John Wiley & Sons, Inc., New York, 1946. They include Idanthrene Rubino RD, Indanthrene Orange RRTA, Idanthrene Golden Orange GA, Idanthrene Brown RA, Helio Fast Yellow 66L,

Indanthrene Brilliant Violet 3BA, Fast Violet 4RN, In

digo Blue, Indanthrene Navy Blue RA. t

(4) Carbon b'lacks Furnace Blacks, Ohannel Blacks, acetylene gas blacks and lamp blacks can also be dispersed by the instant process. t

PIGMENT DISPERSING AGENTS In the improved pigment dispersionjmethod ofthis:

Examples of commercial products are Duponol ME,

which is a dry powder form of sodium lauryl sulfate, manufactured by E. I. du Pont 'de Nemours & Co., and Duponol WA paste, which is a water paste of the same compound, containing 30% active ingredient-and some inorganic salt impurities.

It was 'foundthat the action offatty alcohol sulfates' is greatly enhanced and improved by using as further additive a minor quantity of sodium alkyl'naphthalene" products, such as andv the isobutyl. naphthalene. sulfonate. The former-is marketed u'nd'e-n the trade name of. NekaLA. by the GeneraLDyes'tuif. Corporation and the latter. as. Nekal -DK by the same company. v

Further improvementlin degree of deflocculation, of the pigment, is obtained", by adding protective colloids to the waterdi spersion, such as casein and methylcellulose.

Theproportion of surface active agent/t0, pigment content is've 'mportant. fThe fatty alcohol-sulfates may be added'in proportions of 2' to 20% per 100 parts of drypigment, but for complete deflocculation of the pigment atljeast "and preferably 151to are used. Higher proportions of. fatty alcohol, sulfate are permissible, but do not seem to produce further improvement, in defl'occulation, to a d'egree to Warrant suchincrea'se. Larger proportions maybe used, however, to satisfy specialty purposes'ofj incorporation intofinished products or to satisfy machinery" li'mitations.

The sodium alkyl sulfonates are added in proportions of /2% to 4% based on the pigment content, 2% being a preferred and satisfactory proportion.

If protective colloids are added, about 1% of dry casein is used, based on the dry pigment content and about 5% methyl cellulose low viscosity type, designated as,15 cps. type the trade. Larger quantities of protective colloids can be added, but their action is distinct in the here given proportions. They help to complete deflocculation and keep the particles in suspension.

Theseimproved pigment dispersions. are particularly tion' of thepigment at elevated temperature which ranges from above room temperature to below the boiling: point of water, as foninstance90 C.

PROTECTIVE COLLOIDS In the examples of this specification casein, methylcellulose and sodium carboxymethylcellulose are mentioned assuitabl'e protective colloids. Others which may be usedare: gum tragacanth, dextrin, starch solutions, sodium polyacrylate, sodium polymeth'acrylate, hydroxy ethylcellulose of the, water soluble and alkali soluble types, locust bean gum, water soluble salts of the maleic adduct; of? styrene,v etc.. Algi'nates may be used also.

As! fan as protective colloids. andv emulsifying agents go, care should be exercised that anionic and non-ionic agents and systems may be mixed, and cationic agents and systems may be mixed with non-ionic agents and systems, but cationic and anionic agents or systems normally cause flocculation of. the emulsion or of the pigments.

PROPORTIONS OE INGREDIENTS The proportions of the ingredients of the compositions of this invention, may tolerate certain limits; The examples here below illustrate the process and do not necessarily limit same.

Emulsifying agents-Normally 2 to 6% emulsifying agent is used, based on the dispersed phase. Occasionally larger proportions are of advantage and in some cases somewhat lower quantifies may work. As will be seen in an example of the schematic type, 0.7% emulsitying agent is a typical example, based on the total pigmented resin emulsion. In the t'otalpigment color composition of this invention, the emulsifying agent derived from the resin emulsion ranges from about 0.18% to about 2.1 6%".

Protective c0lloids.'-Many protective colloids exert 8 stabilizing properties inas low" a proportio'rr as of the water phase. The examples here below contain about 4- to 7% of the concentrated-emulsion; In the total pigment color composition of this invention, the protective 'colloid rangesfrom about 0i075'%- to 4.34%. These proportionsdo not include any protective colloid component present in the pigment dispersion. The textile printing colorsof this invention are stable to the degree, that they take repeated freezing; and re-thawing cycles, without damage.

Resin content;-The dispersed phase in many of the resin contents of 15% to 50% are possible in the binder emulsions of this invention. In the total pigment color" composition of this invention, the resin binder content ranges from about 4.5 to about 31%.

Pigment c0ntent.The pigment content in the color concentrates ranges fron1a7 to .22%',..butitmay behigher if fillers or extender pigments: are present. There issome limitation as far as the water. content of presscakesis concerned, when presscakes form: the starting-material: More organic. pigments are hydro-g for the pigments. phobic and presscakes come between 10% to 35% pigment content, depending on' the nature of pigment and method of precipitation. However, if wevstartwith dry pigments; we can regulate the water content, as pigment slurries, properly dispersed; may be-obt'ained aswhi-gh as with pigment content, the rest being. water and" dispcrsingagents as described above, An example ofthi's" isa titaniumdioxide dispersion in water. Thercomposition'of the pigment dispersion is described above under the heading fPigment dispersing agents.

Pigment to binder ratio-In the examples we have about 12 to 12 /2 parts of resin solids and additional protective colloid solids per 7 to 22 parts of pigment: With pigments which crock higher,.larger binder proportions are required, whereas with" pigments with low crock-.-

ranges of 2.8to5.

Many cat-ion. active emulsifyingv agents work better on the acid: side. Also these, requireacid emulsion polymerization.

Theillustrative examples herebelow illustrate the ,process on alkaline side type emulsions and emulsion polymerization. These examples should therefore be consideredto' illustrate the process and not to limitsame.

ILLUSTRATI'V'E' EXAMPLES The here following examples will illustrate the process and products without limiting them. Emulsifying agents,

pH of emulsions, type and percentage of protective col"- loids will be considered" variable, within the described scop'eof this'specification.

ILLUSTRA H-VE EXAMPLES E-polyester binders The E-polyester binders ofv this invention consist of an alcohol component and a fatty acid component.

Alcohol component of E-po lyesters I The alcohol component of .the E-polyestersof this invention are resinous condensation products of epihalohydrins or dihydrins. withpolynuclear phenols, like cp-noct oi a Me being a methyl radical. The most common type of this group is represented by the condensation products of epichlorhydrin with bis-phenol. The following resinous alcohols can be prepared by such condensation:

These products are substantially free of halogens and should be considered as ethylene oxide derivatives of polynuclear phenols, showing free hydroxy groups, which can enter into esterificationreactions.

Fatty acid component of E-polyesters The fatty acid components may be fatty acids'of naturally occurring fats and fatty oils. Examples are: oleic acid, linoleic acid, linolenic acid, clupanodonic acid, dehydrated ricinoleic acid, eleostearic acid, natural mixtures of soyabean fatty acids, sunflower oil fatty acids, linseed oil fatty acids, dehydrated castor oil fatty acids, tung oil fatty acids, stearic acid, palmitic acid, lauric acid, tall oil acids, etc. Rosin may be used to replace part 'of' the fatty acids. carbon atoms in the molecule. Unsaturated fatty acids obtained from drying and semi-drying fatty oils are preferred for this invention, as they reach the thermo-set stage at room temperature or at low temperatures, not exceeding 220 F; at reasonable speed. Linseed oil fatty acids and dehydrated castor oil fatty acids are examples of products with merit in this process. Rosin acids may be present to replace part of the fatty acids. E.g. linseedoil fatty acids and rosin may be combined imultaneously with the alcohol component.

Resinous E-polyesters The following examples are given for the preparation of the E-polyester binders, suitable in the instant process:

EXAMPLE 1 Pounds Alcohol component resin #2, with combining weight of 174 1102 Rosin, W.G. grade 243 Linseed oil fatty acids 1230 Petroleum aromatic solvent with boiling range from 318 to 400 F. and flash point of 100 F. 680 Mineral spirits 681 Total 3936 Loss of water ofesterification 205 Yield 3731 weight of 174 2540 Dehydrated castor oil fatty acids 1695 Xylol 3435 Total 7670 Loss of water of esterification 400 Yield 7270 Esterification reaction starts at 350 to 400 F. Raise 1 temperature from 400 F. to 500 F. in 1.5 to 2 hours, pass inert gas through reaction mixture, holduntil acid Normally these fatty acids have 12 to 24 culation and dispersion. 24 hours to 48 hours are satisnumber is 2. Yield is 898gallons,-nonvolatile" 8.10 lbs/gal, acid number 0.5 to 2, viscosityX:

to Z on Gardner scale. This resin is. further reduced to 50% N.V. with xylol for use in the examples.

Both the resin of Example 1, and that of Example. 2, can be made by the solvent process of esterification, in

thejpresence of small amounts'of solvent, while the sol vent is refluxed and the condensed water separated before the refluxing condensed solvent is returnedto the reaction mixture. Temperature curve has to be adjusted to yield the same constants of the end product.

EXAMPLE 3 42.15 parts of Epolyester resin of Example 2, 0.31 part of mixed naphthenate driers, 12.22 parts of 10% sodium lauryl sulfate solution in water, 20.65 parts of a 20% casein solution in water, containing antifouling agents, 5.48 parts of ammonium hydroxide solution prepared by mixing 1 part of concentrated ammonium hydroxide and 1 part of water, 10.54 parts of a 20% water solution of sodium carboxymethyl-cellulose, low viscosity type and 8.65 parts of water are made into an emulsion in the following manner: Add to the resin solution under agitation /3 of the sodium lauryl sulfate solution, mix the remaining /3, the water and the casein solution in a separate container and add them slowly to the resin solution containing mixture under agitation. Add the ammonium hydroxide solution and add finally the sodium carboxymethylcellulose solution. Homogenize. This emulsion is a suitable binder for color concentrates.

EXAMPLE 4 To a phthalocyanine green press cake, marketed under the trade name of Heliogen Green GV presscake, having 27.6% pigment content Duponol ME dry powder was added to yield 18% Duponol on the pigment content, and Nekal A dry powder was added to yield 2% addition on the pigment content. The press cake was mixed with a spatula by hand; after 5 minutes it became completely liquid. It has been found, that dry powder addition, which is attractive as it does not increase water content, yields very satisfactory results. However, the premixing represents some problem and knife pronged agitators are needed, such as pony mixer blades, to liquefy the press cake to a slurry. Propeller types, or other turbine type agitators, do not work well at this stage as they could not manage to break up the lumps of the press cake. by the aid of an Eppenbach homomixer, which is a high speed turbo mixer, having a narrow clearance between turbine and stator. It runs about 3,600 r.p.m. About 15 minutes is satisfactory, but occasionally up to 30 minutes may be used. A 5 H.P. motored mixer satisfactorily disperses a 500 lb. press cake quantity in a 55 to gal. size drum.

that of Duponol WA paste, i.e., technical sodium lauryl sulfate.

The homomixed slurry is passed through a colloid mill, to complete dispersionand deflocculation. Pebble milling is also very satisfactory to complete pigment deflocfactory milling times.

EXAMPLE 5 Iblue, as described further above in Example 4.

EXAMPLE 6 Example, 3 is repeated, but using E-polyester resin solution of Example 1, after same has been reduced with Mineral Spirits to 50% non-volatile content. The result The premix is then further dispersed- (Open head drum.) The active ingredient in Duponol ME dry powder is the same as like one described, in Example 5.

Emulsion polymerized resin binders I It the re's'in binder is emulsion polymerized or emulsion. aggregated as' described in my copending' application SenaLNo. 739,945, now Patent No. 2,530,370gto'whicl'i this specificationis a continuation-impart, advantagesresult in taster solidifying binders-, increased toughness" andbetter aging qualitiesof'the prints obtained.

EXAMPLE 7" An emulsion-aggregated binder is prepared from the V E-polyester'solut-ion of Example 2, accordingto Example 3 by the fol lowing changesadeducting 3*.58 parts of the water added, and" adding 3.5 8- parts of a 30 volume percent hydrogen peroxide solution to the emulsion at the stage after" the ammonium hydroxide solution wasadded; but before the sodium carboxymethyl-cellulosesolution is added. The'hydrog'en peroxideis' added in increments, wliile t-he emulsion is slowly agitated. The addition of theliydrogen peroxide maybe carried outduring a 2' to 12*hourp'eriod'. The sodium carboxymethylcellulosesolution is added, after the emulsion aggregation process is com pleted.

. I EXAMPLE '8 Example? is repeated with the change that the E-pol'yestersolution of'Example l, is used, reduced to 50% with" MineraPSpirits, instead of the solution of Example 2'. EXAMPLE '9 The product of Example 5 is'repeated With'the alteration' thatthe binderemulsion is an emulsion aggregated mixture of9 %"E-polyester resin solution of Example 2' and 10% of abutyl modified melamine formaldehyde alcohol." A suitable product is Melmac 245=8. The presenceof the melamineresin increases toughness of the film deposited-as a print. 7 V EXAMPLES 10 TO 13 Examples 10 to 13 show the preparation of clear extender printv pastes suitable to adjust the colorstrengthofthe-color concentrates of this invention. The; color concentrates and the extender print pastes can be mixed ini'various proportions to yield cuts of varying color. strength. 'Cuts from 1 to- 1 up to 1:200 are normally used. I

. p EXAMPLE 10 5.90. parts ofthe emulsionof: Example 7, 47.05- parts a 3% .water solution of; 4000 cps. methyl,,cellulos'e, 47.05 partsofwater are mixedandhomogenized. .U'nder agitation witlraasuitable. mixer, like the Eppenbachhomomixer, 100 parts Mineral Spirits, are, stirred into the former emulsionzinzincremcnts. The Mineral Sp'iritsused inthis; example has a bulking value of 0.1515 gallon per pound, a: flashzpoin'tofi;10,0 F., ai-kauri-butanol Value of; 44 to 46, and is marketed under the trade name of Amsco MineralSpirits #46; g

{EXAMPLE 1-1 v 7 To make an; extender print paste similar to-Example but. where the volumetricrelation of. solvent.v to. water phase is changed to yield a lower. solvent-percentage: 23.563 parts of a 3% methylcellulose solution in water, using 4000 cps. methylcellulose, 23.563 parts of water and 21874 parts of. concentrated resin emulsion of EX- ample 7, are mixed and 45.7 l 0j parts of Mineral Spirits of Example 10 are incorporated in a manner as described. in Example 10; The resulting emulsion has a' somewhat lower viscosity than the product of Example 10 i This extender emulsion has about 0.739% methylcellulose', 48.499% Water, 47.739% of solvent and 3.003% reinforcing concentrated resin emulsion.

- EXAMPLE-1'2--RESI'N-FREE EXTENDEE PASTE 0.750 part of400'0 cps. high viscosity m'etliylcellfulbse is dissolved in 49L2S0p'arts' ofwa'ter. 50 parts of Mineral Spiritsof Example-"'10 is incorporated in increments under proper" agitationtained.

. EXAMPLE 1's -EXTENDERPRI T PASTE OF EI'EAMPLE 10, HERE ONE-HALF OF METHYL CELLULOSE IS REPLACED BY. WATER V 0.353 part of 4000 cps. high viscosity methylcelluloseis dissolved in 46.773 parts of water, yielding. an.0.75% methylcellulose solution. This'is' mixed with a concen trated oil-in-water resin emulsion of Example 7, taking 2.874 parts of the latter. The resulting product is agitated and parts 'of Mineral Spirits of Example 10 are incorporated in increments under proper agitation. The 50% lower content in high viscosity methylcell'ulo sef,"its water phase and consequently the emulsion has loWeivis' cosity. The product is a fluid viscous emulsion'with good printingqualities. v

Other extender print pastes, suitable in this invention are described in my; co-pending application Serial No. 180,700, now Patent No. 2,637,705. The, concentrated: resin emulsions in Examples 10, 11 and I3, and in the examples of my co-pending. application. Serial No. 18 0,700,, may be replaced by other concentrated emu-lsions described elsewhere in this specification. EXAMPLE 14'-,SCHEMATIC FORMULA FOR A CONCEN- TRA'l-ED RESIN EMULSION In this example aschematic formula. is given to pre pare aconcentratedresinemulsion suitable in this invention; Resin examples are also listed, which can be satisw factorily used in this schematic formula.

Percent. Resin solution 50% N.V 3 41 .84" Driers, as below 0.63 Pine oil; 0.46: 10% Duponol ME sol. inwater u L 12.111 20% casein sol. in water as below 20.58 Mixture of 50% cone. ammonia and 50% water" 5.40 Low-viscositymethylcellulose solution, as below. 15.44 Hydrogen peroxide" 30 L l -s 3%541 Total 100.00

Non-volatile content 28'.'29

Drier mixture for" schematic formula:

Lead naphthenat'e 24% metal content sol..200

parts b.w. Cobalt naphthenate 6% metal content sol. 25..

. parts b. w. 7 Zinc naphthenate 6% metal content sol. 30

. partsbw;

Casein solution for schematic formula:

Casein, dry 7.75 parts b.w. (Protovac V 8397): t Water' 3 1 part's'bzw. j y i Dowicide A; 010775 part bEW. (1% oncasein); D'owicide'O 0.0775 part bLw. (1;%=on

' casein). Ammonia, cone 0.1163 part b.w. (1.5% on V casein). Lowviscosity methyl cellulose solution forschematic formula: i

Methylcellulose, 15 cps 2.09 parts by wt: Water 13.35 parts by wt.

Order of additio-nin'suitableemulsifying equipment: (1,) Resin solution, drier sol'. pine oil mixed (2) Duponol solution added (3 Casein solution added (-4) Ammonia solution added (5) Hydrogen peroxide added increments (6)= Methylcellulose solutionaddedl A viscous: print. paste lSf Obq ,Methylcellulose solution may be present before hydrogen zperoxide addition. If e.g. sodium carboxymethyl;

cellulose (CMC) replaces methylcellulose it is preferable EXAMPLE 1e-r1'oMnN'r IADDlING,

Because of the lightfastness of pigments and easeof:

their application, to. obtain solid color effects, pigment padding is becoming more and more opular to: replace dyeing. The oil-in-water emulsions of this invention. are

suitable-for pigmentpadding. K The color concentrates of (like Epon 1004) with a mixture of 90% soyabean oil fatty acids and oiticica oil fatty acids and oiticicaoil fatty acids.

Solvents used in above resins are aromatic and/ or aliphatic hydrocarbons. r e e 10 te of resin solution in.the schematic example, may be replaced with amine-aldehyde resins, which contain 50% 'N.V. in solvent mixture of alcohols and hydrocarbons, e.g.: i

Melmac 245-8, butyl modified melamine formaldehyde resin, 50% resin solids, in xylol-butanol solvent mixture; 1 i i Melmac 248-8, butyl modified melamine formaldehyde resin, 55% resinsolids, in xylol-butanol solvent mixture; 1 .1 Y Uformite MM55 butyl modified melamine formaldehyde ",resin, 50% resin solids in xylol-butanol (1:4) solvent mixture; r r Uformite MX61 alkyl modified triazine resin 60% resin solids, in xylol-butanol (1:1) solvent mixture; Uformite F240 alkyl modified urea formaldehyde resin 60% resin solids, in xylol-butanol (121.5) solvent mixture; Beetle 216-8 alkyl modified urea formaldehyde resin 60% resin solids, in xylol-butanol solvent mixture.

The same emulsions with the resins described above, can be prepared without emulsion polymerization, using Water instead of the hydrogen peroxide in the schematic formula. Such emulsions are similar in nature to the one described in Example 3. The films they form will have a shorter life and. the film formation period will be longer, than compared with the emulsion polymerized product. EXAMPLE 15-SCHEMATIC FORMULATIO MENT COLOR .CONCENTRA'IES In the schematic formula for pigment color concentrates I prefer to use 59 parts of concentrated resin emulsion of Example 14, 2.9 parts of polychloroprene latex, 60% nonvolatile, like neoprene 601 latex and pigments in proportions of 7-'9% pigment content in the color concentrate. The pigments may be incorporated in a manner described in Example 5, using pigment dispersions in water similar to that of Example 4..

The following pigments may be used satisfactorily: Yellow: Benzidine Yellow; Orange: Benzidine Orange; Green: Phthalocyanine Green; Blue: Phthalocyanine Blue; or Indanthrene Blue; Maroon: Thioindigo Maroon; Red: Various insoluble azo pigments of the Naphthol AS type couplings; or Thioindigo Reds and Pinks; Brown: various azo browns and vat browns; Greys and Blacks: Carbon Black,such as furnace blacks and channel blacks, gas blacks, bone black, vegetable black, various vat blacks and greys.

The 59 parts of concentrated emulsion contains about 12.3 parts of resin solids, 2.4 parts of casein, 1.2 parts of low viscosity methylcellulose, 0.7 part of emulsifying agent, and 0.09 part of driers.

In this schematic formula the binder to pigment ratio may be changed in a manner that the binder solids are reduced and the pigment solids increased. Color concentrates with pigment content up to 22% and concentrated resin emulsion content down to 30 to 40% may be suitable for many purposes.

or PIG- The use of amine-aldehyde resins helps the formation of thermoset resin films and also assists insolubilization of the protective colloids.

carboxymethylcellulose, sodium or ammonium jalginate,

amongst others. 1 l p In the event low viscosities can betolerated, the amount of protective colloid maybe reduced in the binder emulsion and color concentrate, whereby laundering resistance increases. l v

. There are two difliculties in the way of popularizing pigment padding. One is crocking. The binder emulsions, as formulated above, sow very low erocking and can be considered as practicallynon-crocking for many purposes, thereby :eliminatingthis.drawback of pigment padding. The second difficulty is represented byx the phenomenon called pigment migration. During the dryingoperation the pigments migrate towards the heatand cause s'treaks and unevencolor effects. If the drying tunnels or chambers show the slightest differences in spots with regard to temperature, pigment migration will take place; It is Very difiicult even with the most modern equipment to. have uniform temperatures all over the drying chambers. The emulsion aggregated (emulsion polymerized) binders are solidified in the emulsion and therefore prevent the migration of the pigments. This particular performance of these new emulsions 1 permits their use with great advantage in pigment padding to produce solid color effectsby pigments.

EXAMPLE n-cnooxhnnucris'o stiis'1surs In the above examples neoprene latex was-used as crock reducing agent.

ear polymer of isobutylene), vinyl chloride polymers, acrylonitrile copolymers and mixtures of the last two mentioned polymers. In the col-or concentrates I may use from 0.1% to 2% crock reducing agent solids. In many instances increase in the concentrated resin emulsion content may eliminate the necessity of using a special crock reducing agent. The concentrated resin binder emulsion may be increased, for example, to about 62% by weight based upon the total composition.

EXAMPLE 18WHITE COLOR CONCENTRATE A pigmented white color concentrate is made by pre paring la 70% pigment content titanium dioxide water dispersion, by adding 18% Duponol Me and 2% Nekal A (propylated naphthalene sulfonate) based on the pigment content. The dispersion contains 70% titanium dioxide, 14% wetting agents, and 16% water. The color concentrate is prepared by taking 59 parts of the resin emulsion of Example 7, 2.9 parts of neoprene latex 601, and 38.1 parts of said white pigment slurry (dispersion). This color concentrate may be used to print white on loosely woven fabrics, on light dyed fabrics, or with a discharge extender cutback emulsion as discharge white on predyed background. A 1:2 cut is a satisfactory dilution. This white pigment concentrate when added in small proportion to other colors, will increase their hiding power and enable colored printing effects on light or medium light predyed backgrounds, without discharge.

The color concentrates of this invention, as illustrated by Examples 5,15, 17. and 18, form textile printing color I found that satisfactory crock reduction is obtained with the use of neoprene cements (solvent solutions), polystyrene emulsions, Vistanex (lin-.

compositions in admixture extender print paste emulsions. I i

For each volume part'of color concentrate from about 1 volume part to about 200 volume parts or extender printpaste emulsion may be used in the admixture. These extender print paste emulsions are. illustrated by Examples to 13 and preferably comprise 47.5to 56% water, 0.3 to 0.8% of high viscosity water soluble cellulose ether and 43% to 51.5% of a water immiscible hydrocarbon solvent, said pencents of the extender print paste emulsions being expressed on weight basis,

What is claimed is;

l. The process of preparing an oil-in-Water resin emulsion textile decorating pigment color composition which comprises preparing as a first component anaqu'eous resin emulsion'c'ontaining an esterof a polyunsaturated fatty acid with a synthetic alcohol formed by the condensation of ep'ichlorohydrin and bisphenol as a resin binder, an

emulsifying agent selected from the class consisting of soaps of fatty'acids, fatty acid esters of polyethylene glycols, quaternary ammonium salts, fatty alcohol sulfates, polyethylene oxide condensation products, polyacryla'te, water-soluble and alkali-soluble hydroxyethylcellulose, locust bean'gum, water-soluble salts of the maleic adduct of styrene, and alginates, preparing as a separate second component an' aqueous pigment dispersion containing a'pigment' which is in the in-water deflocculated state and which is a member of the class con sisting 'of phthalocyanine pigments, insoluble azo pigmerits, vat pigments, carbon blacks and titanium dioxide, the particles of said pigment in said separate component beingYsurrounded "by water having dissolved therein a water-soluble-fatty alcohol sulfate as a pigment-dispersing agent, said fatty alcohol sulfate having at least 12 carbon atoms in the molecule and being present in the said separate component in proportions of at least about 10% of the weightof the pigment, and combining said emulsion and said separate component to form a viscous pigment color composition suitable as a color concentrate, which is dilutable with clear extender print paste emulsions to form the desired strength of shade when used for textile printing, said pigment color composition having, based said protective colloid, said resin binder, emulsifying agentand protective colloid all being derived from said first resin emulsion component, and between about 7% and about 22% of said pigment derived from said separate second component." i

'2. 'An'oil-in-water resin emulsion textile decorating claim 1.

3. The composition of claim-2, inwhich the resin binder non-volatile content'comprises from' about 10% to about of an organic solvent soluble amine-form aldehyde resin. i

4. The. composition of claim 2, in which the resin binder non-volatile content comprises from about 10% to about 20% of an organic solvent soluble melamine formaldehyde resin.

5. The composition of claim 2, in which the resin binder non-volatile content comprises from about 10% to about 20% of an organic solvent soluble urea formalde- Hyde resin. i

6. The composition of claim 2, containingin addition pigment color composition prepared by the process of 'organiovolatile hydrocarbon solvents in the dispersed phase. o h mu ion 7. An oil-in-water resin emulsion textile printing color composition consisting of l'part by volume of the color compositionof claim 2 and from about 1 part to about 200 parts by volume'of a clear extender print paste emul sion, said extender print paste emulsion comprising 47 /2 to 56%"water, 0.3% to 0.8% of high viscosity water soluble cell-ulose ether and 43% to SU /2% of' a water iscible hydrocarbon solvent, all percents being by W g A j t 8. The composition of claim 2, in, which the emulsifying agent is a lauryl alcohol sulfate.

9. Thejcomposition of claim 2' in which the pigmentdispersing agent is in the proportion of about 18'parts by weight of fatty alcohol sulfate and of about 2 parts by weight of alkyl naphthalene sillfonate for each parts by weight of dry'pig ment. I:

component contains additionally a protective colloid.- i

11. The, process of preparing an oil-in-water resin emul; siontextile decorating pigment color composition which comprises preparing as a first component an aqueous resin. emulsion containing an ester ofa polyunsaturated fatty. acid with a synthetic alcohol formed by the con densation of epichlorhydrin and bisphenol as a resin binder, an emulsifying agent selected from theclass con; sisting .of soapsof fatty acids, fatty acid esters ofpolyethylene glycols, quaternary ammonium salts, fattyalcohol sulfates, polyethylene oxide condensation products, polymerized glycol estersand sodium salts of organic sulf onates, and a protective colloid, selected from the class consisting of casein, ammonium caseinate, methylcellulose, sodium carboxymethylcellulose, gum tragacanth, dextrin, starch, sodium poly-acrylate, polymethacrylate, water-soluble and alkalisoluble hydroxyethylcellulose, locust bean gum, water-soluble salts of'the maleic adduct of styrene, and alginates, the vehicle solids of the emulsion being sensitive to the action of theair when exposed to air in a thin layer of a wet film thickness of 0.0015 to 0.003" and forming a co herent solid film immediately upon demulsification of the emulsion, said 'solid film formation being reached within a period ranging from a couple of'seconds to one hour, the solid polyhydric alcohol esters in the dispersed phase of theemulsion having an oxygen content not exceeding the oxygen content of the unemulsified polyhydric alcohol esters by more than 2.8%, preparing as .a separate second component an aqueous pigment dispersion containing a pigment which is in the, in-water deflocculated state and which is a member of the class consisting of phthalocyanine pigments, insoluble azo pigments, vat pigments, carbon blacks and titanium dioxide, the particles of said pigment in said a separate component beingsurroundedby water having dissolved therein a water-soluble fatty alcohol sulfate as a pigment-dispersing agent, said fatty alcohol sulfate, havingat least 12 carbon atoms in the molecule and being present in the said separate component in proportions of at least about 10% of the weight of the pig ment, and combining said emulsion and said separate, component to form a viscous pigment color composition suitable asia color concentrate, which is dilutable with clear extender print paste emiulsions, .to form the desired strength of shade when used for textible printing, said pigment color composition having, based on the total weight of said pigment color composition, between about 4.5% and about 31% of said resin binder, between about 0.18% and about 2.16% of said emulsifying agent, between about 0.075% and about 4.34% of said protective colloid, said resin binder, emulsifying agent and protective colloid all being derived from said first resin emulsion component, and between about 7% and about 22% of said pigment derived from said separate second component.

sl in ll,

13. A pigment free oil-in-water emulsion coating material useful as the first component in claim 12 in which the dispersed phase incorporates a resin which is an ester of an unsaturated fatty acid with "a synthetic alcohol formed by the condensation of epichlorhydrin and bis-phenol, said ester being in a solid state in the water emulsion, the vehicle solids of the emulsion being sensitive to the action of the air, when exposed to it in a thin layer of a Wet film thickness of 0.0015 to 0.003", forming a coherent solid film immediately upon demulsification of the emulsion, said solid film formation being reached within a period ranging from a couple of seconds to one hour, the vehicle solids dispersed phase content ranging from 10% to 70%, based on the total weight of water and vehicle solids constituents of the emulsion surface coating material, said emulsion surface coating material comprising further an emulsifying agent selected from the class consisting of soaps of fatty acids, fatty acid esters of polyethylene glycols, quaternary ammonium salts, fatty alcohol sulfates, polyethyleneoxide condensation products, polymerized glycol esters and sodium salts of organic sulfonates in a proportion between about 0.2% and about 4.2% on. said oil-in-water emulsion, and :a protective colloid selected from the class consisting of casein, ammonium caseinate, methylcellulose, sodium carboxyrnethylcellulose, gum tragacanth, dextrin, starch, sodium-polyacryiate, sodium-polymethacrylate, water-soluble salts of the maleic adduct of styrene and alginates in a proportion between about 0.25% and about 7% based on said oil-in-water emulsion.

14. The composition of claim 12, in which the pro tective colloid is methylcellulose.

15. The composition of claim 12, in which the protective colloid is casein.

Auer May 5, 1953 Auer a June 15, 1954 

1. THE PROCESS OF PREPARING AN OIL-IN-WATER RESIN EMULSION TEXTILE DECORATING PIGMENT COLOR COMPOSITION WHICH COMPRISES PREPARING AS A FIRST COMPONENT AN AQUEOUS RESIN EMULSION CONTAINING AN ESTER OF A POLYUNSATURATED FATTY ACID WITH A SYNTHETIC ALCOHOL FOARMED BY THE CONDENSATION OF EPICHLOROHYDRIN AND BISPHENOL AS A RESIN BINDER, AN EMULSIFYING AGENT SELECTED FROM THE CLASS CONSISTING OF SOAPS OF FATTY ACIDS, FATTY ACID ESTERS OF POLYETHYLENE GLYCOLS, QUATERNARY AMMONIUM SALTS, FATTY ALCOHOL FATES, POLYETHYLENE OXIDE CONDENSATION PRODUCTS, POLYMERIZED GLYCOL ESTERS AND SODIUM SALTS OF RGANIC SULFONATES, AND A PROTECTIVE COLLIOD, SELECTED FROM THE CLASS CONSISTING OF CASEIN, AMMONIUM CASEINATE, METHYCELLULOSE, SODIUM CARBOXYMETHYLCELLULOSE, GUM TRAGACANTH, DEXTRIN, STARCH, SODIUM POLYACRYLATE, SODIUM POLYMETHACRYLATE, WATER-SOLUBLE AND ALKALU-SOLUBLE HYDROXYETHYLCELLULOSE, LOCUST BEAN GUM, WAATER-SOLUBLE SALTS OF THE MALEIC ADDUCT OF STYRENE, AND ALGINATES, PREPARING AS A SEPARATE SECOND COMPONENT AN AQUEOUS PIGMENT DISPERSION CONTAINING A PIGMENT WHICH IS IN THE IN-WATER DEFLOCCULATED STATE AND WHICH IS A MEMBER OF THE CLASS CONSISTING OF PHTYALOCYANINE PIGMENTS, INSOLUBLE AZO PIGMENTS, VAT PIGMENTS, CARBON BLACKS AND TITANIUM DIOXIDE THE PARTICLES OF SAID PIGMENT IN SAID SEPARATE COMPONENT BEING SURROUNDED BY WATER HAVING DISSOLVED THEREIN A WATER-SOLUBLE FATTY ALCOHOL SULFATE AS A PIGMENT-DISPERSING AGENT, SAID FATTY ALCOHOL FULFATE HAVING AT LEAST 12 CARBON ATOMS IN THE MOLECULE AND BEING PRESENT IN THE SAID SEPARATE COMPONENT IN PROPORTIONS OF AT LEAST ABOUT 10% OF THE WEIGHT OF THE PIGMENT, AND COMBINING SAID EMULSION AND SAID SEPARATE COMPONENT TO FORM A VISCOUS PIGMENT COLOR COMPOSITION SUITABLE AS A COLOR CONCENTATE, WHICH IS DILUTABLE WITH CLEAR EXTENDER PRINT PASTE EMULSIONS TO FORM THE DESIRED STRENGTH OF SHADE WHEN USED FOR TEXTILE PRINTING, SAID PIGMENT COLOR COMPOSITION HAVING, BASED ON THE TOTAL WEIGHT OF SAID PIGMENT COLOR COMPOSITION, BETWEEN ABOUT 4.5% AND ABOUT 31% OF SAID RESIN BINDER BETWEEN ABOUT 0.18% AND ABOUT 2.16% OF SAID EMULSIFYING AGENT, BETWEEN ABOUT 0.07% AND ABOUT 4.34% OF SAID PROTECTIVE COLLOID, SAID RESIN BINDER, EMULSIFYING AGENT AND PROTECTIVE COLLOID ALL BEING DERIVED FROM SAID FIRST RESIN EMULSION COMPONENT, AND BETWEEN ABOUT 7% AND ABOUT 22% OF SAID PIGMENT DERIVED FROM SAID SEPARATE SECOND COMPONENT. 